CN105820826A - Method of producing fuel oil by thermally decomposing waste toner cartridge carbon powder - Google Patents

Abstract

The invention discloses a method for producing fuel oil by pyrolyzing waste toner cartridge carbon powder. First dry the waste toner cartridge toner, and then heat it in a vacuum environment for high-temperature anaerobic pyrolysis reaction (drying, vacuuming, and heating in sequence) to obtain pyrolysis oil gas and solid residue (the solid residue is residual silica and ferric oxide). The pyrolysis oil gas is the vaporized state of heavy oil, medium oil and light oil. The pyrolysis oil gas is condensed in three stages and segments, and the pyrolysis oil gas components are liquefied step by step and then collected in stages to obtain liquid oil. In the present invention, the process of pyrolysis, condensation and collection of waste toner cartridge carbon powder is carried out continuously and synchronously, and at the same time, the classified collection of pyrolysis oil, gas and solid residue is realized, the toxic organic matter in the carbon powder is harmlessly treated, and the pyrolysis reaction rate is improved. Faster, the quality of fuel oil has been significantly improved, less investment and lower cost, it has filled the gap in recycling waste toner cartridge toner technology, and has significant economic and environmental benefits.

Description

A method for producing fuel oil by pyrolysis of waste toner cartridge toner

technical field

The invention belongs to the technical field of solid waste recycling. More specifically, it relates to a technology for resource utilization of waste toner cartridges, that is, a method for producing fuel oil by pyrolyzing waste toner cartridges.

Background technique

With the accelerated development of electronic information, printers, copiers and fax machines are constantly updated. Toner cartridges are the most frequently replaced consumables, and the number of discarded toner cartridges reaches 75 million per year. The residual amount of toner in a used toner cartridge can reach 7.8%, so there is a large amount of residual toner to be disposed of. Carbon powder is a powder with a particle size of 5-12 μm, and its main components are polyacrylate-styrene, polyethylene/polypropylene paraffin, hydroxyaromatic acid derivatives, ferric oxide, silicon dioxide, etc. Among them, polyacrylate-styrene, polyethylene/polypropylene paraffin, and hydroxyaromatic acid derivatives are carcinogens. Because the particle size of carbon powder is very small, it is easy to disperse into the environment during the recycling process of used toner cartridges, and it will seriously affect the health of the human body after being inhaled by people. If the high-molecular organic matter contained in the components enters the water body or soil, it will permanently pollute the water body and soil, destroy the ecological environment and even enter the biological food chain.

At present, the recycling technology of toner in waste toner cartridges is mainly recycling. Patent "Collection and Treatment Method of Samsung Series Color Toner" (Su Guolin et al., CN104238330A); Patent "Collection and Treatment Method of Brother Series Color Toner" (Su Guolin et al., CN104238331A); Patent "Collection and Treatment Method of HP Series Color Toner" (Su Guolin et al. , CN104238332A) has proposed a kind of waste toner collection processing method, by drying toner, utilize filter screen to carry out coarse screening and fine screening; Carry out the toner cartridge test with good toner of index test, reach the carbon powder of using requirement The powder is reused. This method selectively recycles residual toner, and low-quality residual toner cannot be used because it does not meet the usage standards; the quality of recovered industrial toner varies, and the recycling capacity of waste toner treatment methods for specific brands is limited . In addition, the following invention patents all mention waste toner cartridge toner, but focus on the recycling and collection of waste toner cartridge toner. Problem: Patent "A New Type of Toner Cartridge Recovery Machine" (Yang Jinxu et al., CN204576061U); Patent "Waste Toner Recovery Device" (Li Qionglian, CN201780459U); , CN103488070A); Patent "Toner Cartridge Residual Powder Recovery Machine" (Wu Haifeng, CN202948251U). Furthermore, the patent "Waste Toner Recovery Method, Recovery Device and Its Recycled Plastic" (Li Qionglian, CN102339006A) discloses a method of using waste toner as raw material and cooperating with waste plastic to make recycled plastic; the patent "A Printer , Resource Utilization Method of Waste Toner in Copiers" (Tang Huidong, CN104311879A) discloses a waste toner utilization method, through screening and activation of waste toner, as a substitute for carbon black, it becomes a rubber filling Reinforcing agent. However, the transfer of ferroferric oxide and silicon dioxide in carbon powder to plastics and rubber will affect its quality; the polyester polymer organic matter in carbon powder has not been finally treated, and there is still the possibility of escaping into the environment. be effectively suppressed.

Therefore, it is very necessary to study new carbon powder recycling methods. Pyrolysis technology is a decomposition process in which organic matter is heated in an oxygen-free or oxygen-deficient state to make it into a gaseous, liquid or solid combustible substance. At present, there are few patent applications and related literature reports on recycling technology of waste toner cartridge toner, and there is no report on treating toner in waste toner cartridges through efficient pyrolysis technology.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the defects and insufficiencies of the recycling technology of waste toner cartridges in the above-mentioned prior art, and provide a method for producing fuel oil by pyrolysis of waste toner cartridge toner, so as to realize the waste toner cartridge toner to the greatest extent. resources, but also has the characteristics of high efficiency and environmental friendliness.

The object of the present invention is to provide a method for producing fuel oil by pyrolyzing waste toner cartridge carbon powder.

Another object of the present invention is to provide a system for producing fuel oil by pyrolysis of waste toner cartridge toner.

The above object of the present invention is achieved through the following technical solutions:

A method for producing fuel oil by pyrolysis of waste toner cartridge toner, first drying the waste toner cartridge toner, and then heating in a vacuum environment for high-temperature anaerobic pyrolysis reaction (drying, vacuuming, and heating in sequence) to obtain pyrolysis oil gas and solid residue (the solid residue is residual silicon dioxide and ferric oxide).

Further, after the pyrolysis oil and gas are condensed in stages (the components are liquefied step by step), liquid oil is collected in stages.

Preferably, the pyrolysis oil gas is in the vaporized state of heavy oil, medium oil and light oil, and the segmental condensation is a three-stage segmental condensation, and the condensation temperature is according to the vaporization state of heavy oil, medium oil and light oil The condensation point is set separately.

More preferably, specifically, the above-mentioned method for producing fuel oil by pyrolysis of waste toner cartridge toner comprises the steps of:

S1. Drying and vacuuming: First, send the waste toner cartridge toner into the pyrolysis reactor for drying, and use a vacuum pump to evacuate the pyrolysis reactor to a vacuum state (at this time, ensure that all the toner remains in the pyrolysis reactor );

S2. Heating: Heating with an external heating element, the dried toner cartridge toner is subjected to a high-temperature anaerobic pyrolysis reaction under high vacuum to obtain pyrolysis oil gas and solid residue (the solid residue is residual carbon dioxide silicon and ferric oxide);

S3. Staged condensation: The pyrolysis oil gas enters three condensers for three-stage condensation in turn, and the pyrolysis oil gas components are liquefied and collected step by step.

Wherein, the pyrolysis oil gas described in step S2 is the vaporized state of heavy oil, medium oil and light oil, and the evaporated pyrolysis oil gas and solid residue are separated.

Preferably, during the pyrolysis process of the method of the present invention, the vacuum pump continues to work, and the non-condensable gas is collected in the gas collecting bottle; after the pyrolysis reaction is completed, the remaining solid residue is collected in the storage tank.

Preferably, the condenser adopts a circulating water cooling system, and the condensation temperature of the three condensers is set according to the condensation points of heavy oil, medium oil and light oil.

Specifically, the condensation temperatures of the three condensers are 30-50 degrees Celsius, 170-190 degrees Celsius, and 280-300 degrees Celsius, respectively.

Preferably, the pyrolysis reactor and the condenser are airtight and continuous, ensuring that the pyrolysis reactor and the condenser are in the same vacuum state.

Preferably, the pyrolysis reaction process, the condensation collection process and the non-condensable gas collection process are continuously and synchronously performed.

Preferably, the drying described in step S1 is to make the waste toner cartridge carbon powder lose moisture at a lower temperature, so as to avoid the influence of moisture on pyrolysis products

Preferably, the pumping to a vacuum state in step S1 is pumping to a vacuum degree of 5×10 ^-3 to 1×10 ^-2 Pa.

More preferably, the pumping to a vacuum state in step S1 is pumping to a vacuum degree of 6.7×10 ^-3 Pa.

Preferably, the heating in step S2 is to heat to a temperature not lower than 600 degrees Celsius, and the dried waste toner cartridge toner is subjected to anaerobic pyrolysis reaction under high vacuum and not lower than 600 degrees Celsius.

More preferably, the heating in step S2 is heating to 600-1500 degrees Celsius. The dried waste toner cartridge carbon powder is subjected to anaerobic pyrolysis reaction at a vacuum degree of 5×10 ^-3 to 1×10 ^-2 Pa and at 600 to 1500 degrees Celsius.

Most preferably, the heating in step S2 is heating to 600-1000 degrees Celsius. The dried waste toner cartridge toner is subjected to anaerobic pyrolysis reaction at a vacuum degree of 6.7×10 ^-3 Pa and 600-1000 degrees Celsius.

The technical method of the present invention is to pyrolyze waste toner cartridge carbon powder in a high-temperature vacuum environment, and the polyester polymer organic matter undergoes a carbon bond breaking reaction, and the obtained low-molecular organic matter evaporates rapidly at a high temperature, and silicon dioxide, tetraoxide Separation of three iron solid particles; further condensing the gas obtained by pyrolysis through the condenser in sections, and collecting the liquid oil in sections. The condenser condenses the heavy oil with a higher evaporation point first, followed by the medium oil with a lower evaporation point. Quality oil and light oil; non-condensable gas is finally collected in the gas collecting bottle to realize the continuous separation of different components of waste toner cartridge toner. Specifically, this technology mainly includes the following points:

(1) Send the waste toner cartridge toner into the pyrolysis reactor for drying and vacuuming. At this time, ensure that all the toner remains in the pyrolysis reactor; the pyrolysis reactor is heated by an external heating element, and the pyrolysis The temperature was kept constant during the reaction.

(2) The carbon powder undergoes high-temperature anaerobic pyrolysis reaction under high vacuum, and the polyester polymer organic matter breaks carbon bonds and evaporates rapidly at high temperature to obtain pyrolysis oil gas mainly composed of low molecular organic matter; pyrolysis oil gas and The solid particles of silicon dioxide and ferric oxide are separated.

(3) Enter the condenser through the delivery pipeline for three-stage condensation, and the components in the pyrolysis oil gas are liquefied step by step and collected in the oil storage tank in sections. The temperature setting of the condenser is the key to collecting liquid oil in stages, ensuring that the gas temperature at the outlet of the condenser is higher than the set condensation temperature.

(4) During the pyrolysis reaction process, the vacuum pump continues to work, and the non-condensable gases mainly including methane, ethylene, propylene, etc. are collected in the gas collecting bottle under the pumping action of the vacuum pump. After the pyrolysis reaction, solid residues such as silicon dioxide and ferric oxide in the reactor are collected in the storage tank under the suction of the powder suction pump.

In addition, a system for producing fuel oil by pyrolyzing waste toner cartridge toner includes a pyrolysis reactor, a primary condenser, a secondary condenser, a tertiary condenser and a vacuum device connected in sequence through a delivery pipe.

Using this system to pyrolyze the waste toner cartridge toner to produce fuel oil, first send the waste toner cartridge toner into the pyrolysis reactor for drying; use the vacuum pump to vacuum the inside of the pyrolysis reactor; then use the external heating element to heat; Drying, vacuuming, and heating processes are carried out in sequence. Carbon powder is subjected to high-temperature anaerobic pyrolysis reaction under high vacuum to obtain pyrolysis oil gas and residual silicon dioxide and ferric oxide solid residue respectively; pyrolysis oil gas is mainly the product of heavy oil, medium oil and light oil In the vaporized state, it is sent to the three-stage condenser through the oil and gas delivery pipe for three-stage condensation; the condensation temperature of the three condensers is set according to the condensation point of heavy oil, medium oil and light oil, and the temperature of the condenser The setting is the key to the segmented collection of liquid oil. The pyrolysis oil and gas components are liquefied and collected step by step; the vacuum pump continues to work during the pyrolysis process, and the non-condensable gas is collected in the gas collection bottle; after the pyrolysis reaction is completed, the residual The solid residue is collected in the storage tank.

The present invention has the following beneficial effects:

(1) In the present invention, the pyrolysis, condensation, and collection processes of the waste toner cartridge toner are carried out simultaneously, different components in the toner are classified and collected, and toxic organic substances in the toner are harmlessly treated;

(2) The present invention puts the waste toner cartridge carbon powder under high vacuum and high temperature conditions, shortens the residence time of the carbon powder in the high temperature area, and has a fast pyrolysis reaction rate, avoiding the problem of high impurity content in fuel oil and wide carbon number distribution. problem; with the three-stage condensation, the quality of fuel oil has been significantly improved;

(3) The present invention does not need to add other substances, has low investment and low cost, and fills the blank of waste toner cartridge toner recycling technology, has significant economic and environmental benefits, and has broad application prospects.

Description of drawings

Fig. 1 is the process flow diagram of the method for producing fuel oil by pyrolysis of waste toner cartridge carbon powder in the present invention; wherein: 1 is waste carbon powder; 2 is pyrolysis reactor; 3 is remaining solid residue; 4 is pyrolysis oil gas; 5 6 is the second-level condensation; 7 is the third-level condensation; 8 is the vacuum device (such as a vacuum pump); 9 is the non-condensable gas; 10 is the oil and gas delivery pipe.

detailed description

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

Example 1

A method for pyrolyzing waste toner cartridge carbon powder to produce fuel oil, comprising the steps of:

S1. Drying and vacuuming: First, send the waste toner cartridge toner into the pyrolysis reactor for drying, and use a vacuum pump to evacuate the pyrolysis reactor to a vacuum state (at this time, ensure that all the toner remains in the pyrolysis reactor ), namely 6.7×10 ^-3 Pa vacuum; the evaporated water is pumped out of the device under pre-vacuum conditions;

S2. Heating: Use an external heating element to heat to a temperature ≥ 600 degrees Celsius. The dried waste toner cartridge toner is subjected to a high-temperature anaerobic pyrolysis reaction under high vacuum to obtain pyrolysis oil gas and solid residue (the solid residue for residual silicon dioxide and ferric oxide);

S3. Staged condensation: The pyrolysis oil gas enters the condenser for three-stage condensation, and the pyrolysis oil gas components are liquefied and collected step by step.

Wherein, the pyrolysis oil gas described in step S2 is the vaporized state of heavy oil, medium oil and light oil, and the evaporated pyrolysis oil gas and solid residue are separated.

This technology is to pyrolyze the waste toner cartridge toner in a high-temperature vacuum environment, and the polyester polymer organic matter undergoes a carbon bond breaking reaction, and the obtained low-molecular organic matter evaporates rapidly at high temperature, and solidified with silicon dioxide and ferric oxide. Particle separation; the gas obtained by pyrolysis is further condensed in stages through the condenser, and the liquid oil obtained is collected in stages. The condenser condenses the heavy oil with a higher evaporation point first, followed by the medium oil with a lower evaporation point and Light oil; non-condensable gas is finally collected in the gas collecting bottle to realize the continuous separation of different components of waste toner cartridge toner. Specifically, this technology mainly includes the following points:

(1) Send the waste toner cartridge toner into the pyrolysis reactor for drying and vacuuming. At this time, ensure that all the toner remains in the pyrolysis reactor; the pyrolysis reactor is heated by an external heating element, and the pyrolysis The temperature was kept constant during the reaction.

(2) The carbon powder undergoes high-temperature anaerobic pyrolysis reaction under high vacuum, and the polyester polymer organic matter breaks carbon bonds and evaporates rapidly at high temperature to obtain pyrolysis oil gas mainly composed of low molecular organic matter; pyrolysis oil gas and The solid particles of silicon dioxide and ferric oxide are separated.

(3) Enter the condenser through the delivery pipeline for three-stage condensation, and the components in the pyrolysis oil gas are liquefied step by step and collected in the oil storage tank in sections. The temperature setting of the condenser is the key to collecting liquid oil in stages, ensuring that the gas temperature at the outlet of the condenser is higher than the set condensation temperature.

(4) During the pyrolysis reaction process, the vacuum pump continues to work, and the non-condensable gases mainly including methane, ethylene, propylene, etc. are collected in the gas collecting bottle under the pumping action of the vacuum pump. After the pyrolysis reaction, solid residues such as silicon dioxide and ferric oxide in the reactor are collected in the storage tank under the suction of the powder suction pump.

Example 2

A system for producing fuel oil by pyrolyzing waste toner cartridge toner, the process flow is shown in Figure 1.

Send the waste toner cartridge toner into the pyrolysis reactor (2) for drying; use the vacuum pump (8) to evacuate the interior of the pyrolysis reactor; use an external heating element for heating. Drying, vacuuming, and heating processes are carried out in sequence.

Carbon powder is subjected to high-temperature anaerobic pyrolysis reaction under high vacuum to obtain pyrolysis oil gas and residual silicon dioxide and ferroferric oxide solid residue (3); pyrolysis oil gas is mainly heavy oil, medium oil and light oil The vaporized state of the heavy oil is sent to the condenser through the oil and gas delivery pipe for three-stage condensation (5, 6, 7); the condensation temperature of the three condensers is set according to the condensation of heavy oil, medium oil and light oil Based on this point, the temperature setting of the condenser is the key to the staged collection of liquid oil, and the pyrolysis oil and gas components are liquefied and collected step by step; the vacuum pump continues to work during the pyrolysis process, and the non-condensable gas (9) is collected in the gas collection In the bottle; after the pyrolysis reaction is completed, the remaining solid residue is collected in a storage tank.

According to the method of the present invention, the C/H ratio and C/O ratio of the carbon powder can be increased by adopting the drying method, so as to reduce the generation of secondary products such as coke and carbon dioxide. The silicon dioxide and ferric oxide particles in the carbon powder component act as the coagulation core, and can be used as the carrier for the secondary product coke to adhere to, reducing the coke adhesion on the inner surface of the reactor.

According to the method of the invention, the pyrolysis reaction and the condensation recovery process are carried out synchronously and continuously, and the pyrolysis oil gas obtained from the pyrolysis reaction enters the condenser for three-stage condensation. The three condensers are connected in series, and the liquefaction and collection of oil and gas in the condensers of each stage are carried out separately, and the temperature setting and control of the condensers of each stage is the key.

Example 3

1. Obtain and collect waste toner cartridge toner from a solid waste treatment center, take 300g of toner sample, send it into the pyrolysis reactor, use the system described in Example 2 to carry out pyrolysis, and set the pyrolysis temperature at 700 degrees Celsius. The first-stage condensation temperatures were set to 40 degrees Celsius, 180 degrees Celsius, and 290 degrees Celsius, respectively. Finally, three kinds of oil and gas are obtained.

2. The polyester substances in the toner components of waste toner cartridges are mainly polyacrylate-polystyrene. oil, light oil for oil analysis.

The results show that the yield of heavy oil is small, and the components include a small amount of styrene and acrylate polymers, which may be caused by melting and evaporation during the heating process; the components of medium oil are mainly styrene monoliths. body, acrylate monomer and its derivatives; light oil contains various olefins.

3. In addition, after testing, the obtained heavy oil, medium oil and light oil are of good quality.

Claims (10)

1. A method for producing fuel oil by pyrolysis of waste toner cartridge carbon powder is characterized in that first the waste toner cartridge toner powder is dried, then heated in a vacuum environment to carry out high-temperature anaerobic pyrolysis reaction to obtain pyrolysis oil gas and solid residue. 2. The method for producing fuel oil by pyrolysis of waste toner cartridge toner according to claim 1, characterized in that the pyrolysis oil gas is condensed in stages and collected in stages to obtain liquid oil. 3. according to the method for producing fuel oil by pyrolysis of waste toner cartridge carbon powder according to claim 2, it is characterized in that, the pyrolysis oil gas is the vaporized state of heavy oil, medium oil and light oil, and the subsection condensation It is a three-stage segmental condensation, and the condensation temperature is set according to the condensation points of heavy oil, medium oil and light oil. 4. according to the method for producing fuel oil by pyrolysis of waste toner cartridge carbon powder described in any one of claims 1 to 3, it is characterized in that, comprising the steps: S1. Drying and vacuuming: First, send the waste toner cartridge toner into the pyrolysis reactor for drying, and then evacuate the inside of the pyrolysis reactor to a vacuum state; S2. Heating: Heating with an external heating element, the dried toner cartridge toner is subjected to a high-temperature anaerobic pyrolysis reaction under high vacuum, and pyrolysis oil gas and solid residue are obtained respectively; S3. Staged condensation: The pyrolysis oil gas enters three condensers for three-stage condensation in turn, and the pyrolysis oil gas components are liquefied and collected step by step. 5. according to the method for producing fuel oil by pyrolysis of the waste toner cartridge carbon powder described in claim 4, it is characterized in that, in the pyrolysis process, the vacuum pump continues to work, and the non-condensable gas is collected in the gas collecting bottle; after the pyrolysis reaction ends, the The remaining solid residue is collected in a storage tank. 6. according to the method for producing fuel oil by pyrolysis of waste toner cartridge carbon powder described in claim 4, it is characterized in that, described condenser adopts circulating water cooling system, and the condensation temperature of three condensers is according to heavy oil, medium oil and condensation point setting for light oils. 7. according to the method for producing fuel oil by pyrolysis of waste toner cartridge carbon powder described in claim 4, it is characterized in that, described pyrolysis reactor and condenser are airtight and continuous, guarantee that pyrolysis reactor and condenser are in the same Vacuum state. 8. The method for producing fuel oil by pyrolysis of waste toner cartridge toner according to claim 4, characterized in that, the pyrolysis reaction process, the condensation collection process and the non-condensable gas collection process are continuously and synchronously carried out. 9. The method for producing fuel oil by pyrolysis of waste toner cartridge toner according to claim 4, characterized in that, in step S1, the pumping to a vacuum state is pumping to a vacuum degree of 5×10 ^-3 ~ 1×10 ^-2 Pa. 10. The method for producing fuel oil by pyrolysis of waste toner cartridge toner according to claim 4, characterized in that the heating in step S2 is to a temperature not lower than 600 degrees Celsius.